CN116902963B - Carbon nano tube using pentacarbonyl iron liquid as raw material and preparation process thereof - Google Patents
Carbon nano tube using pentacarbonyl iron liquid as raw material and preparation process thereof Download PDFInfo
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- CN116902963B CN116902963B CN202311176592.8A CN202311176592A CN116902963B CN 116902963 B CN116902963 B CN 116902963B CN 202311176592 A CN202311176592 A CN 202311176592A CN 116902963 B CN116902963 B CN 116902963B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 158
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 115
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 115
- 239000007788 liquid Substances 0.000 title claims abstract description 79
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 88
- 238000000197 pyrolysis Methods 0.000 claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 22
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000000523 sample Substances 0.000 claims description 23
- 239000001307 helium Substances 0.000 claims description 22
- 229910052734 helium Inorganic materials 0.000 claims description 22
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 22
- 239000011812 mixed powder Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 20
- 230000005484 gravity Effects 0.000 claims description 20
- 239000003595 mist Substances 0.000 claims description 20
- 238000005507 spraying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 239000002912 waste gas Substances 0.000 claims description 12
- 230000006835 compression Effects 0.000 claims description 11
- 238000007906 compression Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000000889 atomisation Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 description 41
- 239000010439 graphite Substances 0.000 description 41
- 230000005540 biological transmission Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/17—Purification
Abstract
The invention provides a carbon nano tube taking pentacarbonyl iron liquid as a raw material and a preparation process thereof. The preparation process of the carbon nanotube with pentacarbonyl iron liquid as material includes the following steps: dispersing pentacarbonyl iron liquid in absolute ethyl alcohol and mixing with an organic modifier; atomizing and colliding and mixing with carbon monoxide; providing acetylene and air premixed flame for pyrolysis; hydrochloric acid is added to remove impurities and the mixture is washed. According to the invention, the pentacarbonyl iron liquid is firstly mixed with the absolute ethyl alcohol, and then the organic modifier triethylene glycol and tri-n-octyl phosphine oxide are uniformly mixed to prepare the pentacarbonyl iron dispersion liquid, so that the pentacarbonyl iron dispersion liquid is uniformly dispersed in the pyrolysis process after atomization, the number of carbon nanotubes prepared by pyrolysis is more, the pore distribution is uniform and the pore diameters are consistent, and the effect of improving the quality of the carbon nanotubes is achieved.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a carbon nano tube taking pentacarbonyl iron liquid as a raw material and a preparation process thereof.
Background
The carbon nanotube is a novel nano material with unique characteristics of graphite crimp structure, small diameter, high surface ratio and the like, has special performances in the aspects of electricity, mechanics, heat, optics and the like, and is widely applied to the fields of nano electronic equipment, gas absorption media, field emission displays and the like.
At present, there is a method for preparing carbon nanotubes by flame synthesis, which has three elements of heat source, carbon source and catalyst, and can synthesize the carbon nanotubes in the atmosphere at normal pressure, without vacuum and protective atmosphere, the reaction and synthesis processes are easy to control and the cost is low, and continuous production can be realized, but when carbon monoxide is used as the carbon source and pentacarbonyl iron liquid is directly used as the catalyst for pyrolysis to prepare the carbon nanotubes, the pentacarbonyl iron liquid is difficult to uniformly disperse and agglomerate, thus resulting in less number of the prepared carbon nanotubes and uneven tube hole distribution, and the carbon nanotubes have poor quality.
Therefore, we provide a carbon nanotube with a plurality of tubes and uniformly distributed tube holes, which uses pentacarbonyl iron liquid as raw material, and its preparation process, so as to improve the quality of the carbon nanotube.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a carbon nano tube taking pentacarbonyl iron liquid as a raw material and a preparation process thereof.
A preparation process of carbon nanotubes by taking pentacarbonyl iron liquid as a raw material comprises the following steps:
s1: dispersing pentacarbonyl iron liquid with absolute ethyl alcohol and mixing with organic modifier
Stirring and mixing absolute ethyl alcohol and pentacarbonyl iron liquid, adding an organic modifier, stirring and mixing, and performing ultrasonic treatment to obtain pentacarbonyl iron dispersion;
s2: atomized and collided with carbon monoxide
Atomizing the pentacarbonyl iron dispersion liquid, carrying the pentacarbonyl iron dispersion liquid into a mixing bin by hydrogen, and carrying out collision mixing with carbon monoxide to obtain mixed gas;
s3: providing acetylene and air premixed flame for pyrolysis
Carrying the mixed gas into a pyrolysis chamber through helium, and then providing a heat source for the pyrolysis chamber through premixed flame of acetylene and oxygen for pyrolysis to obtain carbon nano tube mixed powder;
s4: adding hydrochloric acid to remove impurities and washing
Adding hydrochloric acid into the carbon nano tube mixed powder, stirring while performing impurity removal reaction, filtering, washing with deionized water, and drying to obtain carbon nano tube powder.
Further, the anhydrous ethanol in the step S1 disperses pentacarbonyl iron liquid and mixes with an organic modifier, and the method specifically comprises the following steps of
S1.1: putting the mixing box into a circulating water tank, and then introducing 10-20 ℃ circulating water into the circulating water tank to maintain the inside of the mixing box at 10-20 ℃;
s1.2: adding the anhydrous ethanol and the pentacarbonyl iron liquid into a mixing box together according to the ratio of 50-60ml to 1g, and stirring for 20-30min at the speed of 200-300r/min by using a stirrer;
s1.3: adding the organic modifier into a mixing box according to the volume ratio of the absolute ethyl alcohol to the organic modifier of 20-30:1, adjusting the speed of a stirrer to 500-800r/min, continuously stirring for 1-2h, carrying out ultrasonic treatment for 5-10min by using an ultrasonic probe, and uniformly mixing to obtain the pentacarbonyl iron dispersion liquid.
Further, the atomization in the step S2 and collision mixing with carbon monoxide specifically comprises the following steps:
s2.1: adding the iron pentacarbonyl dispersion liquid prepared in the step S1.3 into an atomizer, and atomizing the iron pentacarbonyl dispersion liquid into mist droplets through the atomizer;
s2.2: spraying hydrogen into the atomizer through the first compression spray gun, carrying mist droplets through the hydrogen and spraying into the mixing bin from the left side of the mixing bin, and simultaneously spraying carbon monoxide into the mixing bin from the right side of the mixing bin through the second compression spray gun;
s2.3: the atomized liquid drops carried by the hydrogen collide with the carbon monoxide in the mixing bin and are fully and uniformly mixed to obtain the mixed gas.
Further, the step S3 of providing acetylene and air premixed flame for pyrolysis specifically comprises the following steps:
s3.1: pressing helium into the mixing bin from bottom to top at the speed of 0.6-0.8L/min by an air pump, and carrying the mixed gas prepared in the step S2.3 to continuously flow upwards after the helium enters the mixing bin;
s3.2: until the pressure sensor passes through the central tube of the heating furnace and contacts the pressure sensor at the air inlet valve at the bottom of the heating furnace, when the pressure sensor detects that the pressure at the air inlet valve rises, the pressure sensor sends a signal to the controller;
s3.3: after receiving the signal sent by the pressure sensor, the controller controls the air inlet valve to be opened, and controls the fire feeders at two sides of the heating furnace to respectively provide acetylene and air premixed flames at 0.5-0.8L/min and 2-3L/min from two sides of the heating furnace;
s3.4: helium carries the mixed gas to enter a pyrolysis chamber of a heating furnace, acetylene and air premixed flame burns outside the pyrolysis chamber to provide a heat source for the pyrolysis chamber, and carbon nano tube mixed powder is obtained after pyrolysis for 3-5 hours.
Further, the step S4 of adding hydrochloric acid to remove impurities and washing specifically comprises the following steps:
s4.1: after the carbon nano tube mixed powder prepared in the step S3.4 is cooled to room temperature along with the furnace, a discharge valve of the heating furnace is opened, and the carbon nano tube mixed powder is put into a filter;
s4.2: until the gravity sensor in the filter detects that the gravity in the filter is no longer increased, the gravity sensor sends a signal to the controller;
s4.3: after the controller receives the signal sent by the gravity sensor, the feeding component is controlled to add hydrochloric acid into the filter, and meanwhile, the stirring device in the filter is controlled to stir for 3-5 hours at the speed of 400-500r/min, and impurity removal reaction is carried out to obtain suspension;
s4.4: the controller controls the stirring device to stop stirring, controls the filter to start and controls the liquid outlet valve to open, and filters the suspension;
s4.5: after the filtrate is completely discharged, the controller controls the liquid outlet valve to be closed, deionized water is added into the filter, the filter residue is washed for a plurality of times, and the pH value of the discharged filtrate is detected after the filtrate is discharged after washing each time;
s4.6: stopping washing again until the pH detector detects that the pH of the discharged filtrate is=6-7, and putting filter residues into a baking oven for baking to obtain the carbon nano tube powder.
Further, in the pyrolysis process of the heating furnace in the step S3.4, the waste gas after pyrolysis is collected through the waste gas collecting box at the top of the heating furnace, until the temperature sensor in the waste gas collecting box detects that the waste gas is cooled to 150-200 ℃, the temperature sensor sends a signal to the controller, and after receiving the signal sent by the temperature sensor, the controller controls the air pump to introduce the waste gas cooled in the waste gas collecting box into the oven in the step S4.6, and the washed wet carbon nano tube powder is dried.
Further, the organic modifier is prepared by mixing triethylene glycol and tri-n-octyl phosphine oxide according to the mass ratio of 1-3:1.
Further, the flow rate of hydrogen is 0.2-0.4L/min, the flow rate is 0.2-0.3m/s, the flow rate of carbon monoxide is 0.5-0.6L/min, and the flow rate is 0.3-0.4m/s.
Further, the carbon nanotube with pentacarbonyl iron liquid as the material is prepared through the process of preparing the carbon nanotube with pentacarbonyl iron liquid as the material.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the pentacarbonyl iron liquid is firstly mixed with the absolute ethyl alcohol, and then the organic modifier triethylene glycol and tri-n-octyl phosphine oxide are uniformly mixed to prepare the pentacarbonyl iron dispersion liquid, so that the pentacarbonyl iron dispersion liquid is uniformly dispersed in the pyrolysis process after atomization, the number of carbon nanotubes prepared by pyrolysis is more, the pore distribution is uniform and the pore diameters are consistent, and the effect of improving the quality of the carbon nanotubes is achieved.
2. According to the invention, the atomized liquid drops which are atomized by carrying the pentacarbonyl iron dispersion liquid with the hydrogen are collided and mixed with the carbon monoxide gas, so that the atomized liquid drops and the carbon monoxide are mixed more uniformly, the crystallinity of the prepared carbon nano tube is better, the collimation degree of the carbon nano tube and the graphite lamellar is better, and the spacing between the graphite lamellar is uniform.
3. According to the invention, after the carbon nano tube mixed powder is prepared through pyrolysis, the carbon nano tube mixed powder is added into hydrochloric acid for reaction to remove impurities, and after washing by deionized water, the carbon nano tube with higher purity can be prepared.
Drawings
Fig. 1 is a flow chart of a process for preparing carbon nanotubes using pentacarbonyl iron liquid as a raw material according to an embodiment of the present invention.
FIG. 2 is a summary of experimental test results for examples 1-3 of the present invention.
FIG. 3 is a summary of experimental test results of example 1 and comparative example 1 of the present invention.
FIG. 4 is a summary of experimental test results of inventive example 1 and comparative example 2.
FIG. 5 is a summary of experimental test results of inventive example 1 and comparative example 3.
Fig. 6 is a cold field emission scanning electron microscope (sem) chart of the carbon nanotube according to example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The preparation process of the carbon nanotube with pentacarbonyl iron liquid as the material includes the following steps:
s1: dispersing pentacarbonyl iron liquid with absolute ethyl alcohol and mixing with organic modifier
Putting the mixing box into a circulating water tank, introducing circulating water at 10 ℃ into the circulating water tank to maintain the temperature inside the mixing box at 10 ℃, then adding 50ml of absolute ethyl alcohol and 1g of pentacarbonyl iron liquid into the mixing box together, stirring for 20min at a speed of 200r/min by using a stirrer, finally adding 2.5ml of organic modifier prepared by mixing triethylene glycol and tri-n-octyl phosphine oxide according to a mass ratio of 1:1 into the mixing box, adjusting the speed of the stirrer to 500r/min, continuing stirring for 1h, carrying out ultrasonic treatment for 5min by using an ultrasonic probe, and uniformly mixing to obtain pentacarbonyl iron dispersion;
s2: atomized and collided with carbon monoxide
Adding the pentacarbonyl iron dispersion liquid into an atomizer, atomizing the pentacarbonyl iron dispersion liquid into mist droplets through the atomizer, spraying hydrogen with the flow rate of 0.2L/min and the flow rate of 0.2m/s into the atomizer through a first compression spray gun, carrying the mist droplets through the hydrogen and spraying the mist droplets into a mixing bin from the left side of the mixing bin, and simultaneously spraying carbon monoxide into the mixing bin from the right side of the mixing bin through a second compression spray gun with the flow rate of 0.5L/min and the flow rate of 0.3m/s, wherein the hydrogen carries the mist droplets to collide with the carbon monoxide in the mixing bin, and fully and uniformly mixing to obtain a mixed gas;
s3: providing acetylene and air premixed flame for pyrolysis
The method comprises the steps that helium is pressed into a mixing bin from bottom to top at 0.6L/min through an air pump, after the helium enters the mixing bin, the helium carries the mixed gas to continue to flow upwards until the helium passes through a central tube of a heating furnace and contacts a pressure sensor at an air inlet valve at the bottom of the heating furnace, when the pressure sensor detects that the pressure at the air inlet valve rises, the pressure sensor sends a signal to a controller, the controller receives the signal sent by the pressure sensor, controls the air inlet valve to be opened, controls a flame supplier at two sides of the heating furnace to respectively provide acetylene and air premixed flame for the furnace from two sides of the heating furnace at 0.5L/min and 2L/min, then the helium carries the mixed gas to enter a pyrolysis chamber of the heating furnace, the acetylene and the air premixed flame burns outside the pyrolysis chamber to provide a heat source for the pyrolysis chamber, and after pyrolysis for 3h, carbon nano tube mixed powder is obtained;
s4: adding hydrochloric acid to remove impurities and washing
After the carbon nano tube mixed powder is cooled to room temperature along with the furnace, a discharge valve of the heating furnace is opened, the carbon nano tube mixed powder is put into the filter until a gravity sensor in the filter detects that the gravity in the filter is not increased any more, the gravity sensor sends a signal to a controller, the controller receives the signal sent by the gravity sensor, controls a feeding component to add hydrochloric acid into the filter, simultaneously controls a stirring device in the filter to stir for 3 hours at the speed of 400r/min for impurity removal reaction, so as to obtain suspension, then controls the stirring device to stop stirring, controls the filter to start and controls a liquid outlet valve to open, filters the suspension until the filtrate is completely discharged, controls the liquid outlet valve to close, deionized water is added into the filter, the filter residue is washed for a plurality of times, the pH value of the discharged filtrate is detected after the filtrate is washed each time, until the pH value of the discharged filtrate is detected to be=6, the filter residue is stopped from washing again, and the filter residue is put into an oven for drying, so as to obtain the carbon nano tube powder.
Then, experimental tests were performed on the above carbon nanotube powder:
firstly, adding 5g of carbon nano tube powder into 50ml of absolute ethyl alcohol, oscillating for 10min by using ultrasonic waves to uniformly disperse the carbon nano tube powder, standing and layering for 25min, then dripping 1ml of supernatant onto a copper mesh grid, and drying to obtain a sample;
then, as shown in fig. 6, scanning electron microscope analysis is performed on the sample by using a cold field emission scanning electron microscope, and observation results: the number of the carbon nanotubes is large, the tube holes are uniformly distributed, impurity particles are not attached to the top ends of the carbon nanotubes, the outer diameter length of the tubes is estimated through scanning electron microscope analysis, and the outer diameter range of the tubes is estimated to be about 1nm according to the formula of the outer diameter range of the tubes = the outer diameter of the longest tube-the outer diameter of the shortest tube;
finally, the transmission electron microscope is used for carrying out transmission electron microscope analysis on the sample, and the observation results show that: the carbon nano tube has good crystallinity and good collimation degree of the carbon nano tube and the graphite layer, the distance between two adjacent graphite sheets is estimated by a transmission electron microscope, and the graphite sheet distance range is about 0.02nm according to the formula of graphite sheet distance range = longest graphite sheet distance-shortest graphite sheet distance.
Example 2
The preparation process of the carbon nanotube with pentacarbonyl iron liquid as the material includes the following steps:
s1: dispersing pentacarbonyl iron liquid with absolute ethyl alcohol and mixing with organic modifier
Putting the mixing box into a circulating water tank, introducing circulating water at 15 ℃ into the circulating water tank to maintain the temperature inside the mixing box at 15 ℃, then adding 55ml of absolute ethyl alcohol and 1g of pentacarbonyl iron liquid into the mixing box together, stirring for 25min at a speed of 250r/min by using a stirrer, finally adding 2.2ml of organic modifier prepared by mixing triethylene glycol and tri-n-octyl phosphine oxide according to a mass ratio of 2:1 into the mixing box, adjusting the speed of the stirrer to 650r/min, continuing stirring for 1.5h, carrying out ultrasonic treatment for 7min by using an ultrasonic probe, and uniformly mixing to obtain pentacarbonyl iron dispersion;
s2: atomized and collided with carbon monoxide
Adding the pentacarbonyl iron dispersion liquid into an atomizer, atomizing the pentacarbonyl iron dispersion liquid into mist droplets through the atomizer, spraying hydrogen with the flow rate of 0.3L/min and the flow rate of 0.25m/s into the atomizer through a first compression spray gun, carrying the mist droplets through the hydrogen and spraying the mist droplets into a mixing bin from the left side of the mixing bin, and simultaneously spraying carbon monoxide into the mixing bin from the right side of the mixing bin through a second compression spray gun with the flow rate of 0.55L/min and the flow rate of 0.35m/s, wherein the hydrogen carries the mist droplets to collide with the carbon monoxide in the mixing bin, and fully and uniformly mixing to obtain a mixed gas;
s3: providing acetylene and air premixed flame for pyrolysis
The helium is pressed into the mixing bin from bottom to top at 0.7L/min through the air pump, after entering the mixing bin, the helium carries the mixed gas to continue to flow upwards until passing through the central tube of the heating furnace and contacting with the pressure sensor at the air inlet valve at the bottom of the heating furnace, when the pressure sensor detects the pressure rising at the air inlet valve, the pressure sensor sends a signal to the controller, after receiving the signal sent by the pressure sensor, the controller controls the air inlet valve to be opened, and controls the fire feeders at two sides of the heating furnace to respectively provide acetylene and air premixed flame into the heating furnace from two sides of the heating furnace at 0.65L/min and 2.5L/min, then, the helium carries the mixed gas to enter the pyrolysis chamber of the heating furnace, the acetylene and the air premixed flame burns outside the pyrolysis chamber to provide a heat source for the pyrolysis chamber, and the carbon nano tube mixed powder is obtained after pyrolysis for 3-5 h;
s4: adding hydrochloric acid to remove impurities and washing
After the carbon nano tube mixed powder is cooled to room temperature along with the furnace, a discharge valve of the heating furnace is opened, the carbon nano tube mixed powder is put into the filter, until a gravity sensor in the filter detects that the gravity in the filter is not increased any more, the gravity sensor sends a signal to a controller, after the controller receives the signal sent by the gravity sensor, the controller controls a feeding component to add hydrochloric acid into the filter, simultaneously controls a stirring device in the filter to stir for 4 hours at the speed of 450r/min, a impurity removal reaction is carried out, a suspension is obtained, then the controller controls the stirring device to stop stirring, controls the filter to start and control a liquid outlet valve to open, the suspension is filtered, until the filtrate is completely discharged, the controller controls the liquid outlet valve to be closed, deionized water is added into the filter, the filter residue is washed for many times, the pH value of the discharged filtrate is detected after the filtrate is washed each time, until the pH detector detects the pH=6.5 of the discharged filtrate, the secondary washing is stopped, and the filter is put into a drying oven to obtain the carbon nano tube powder.
Then, experimental tests were performed on the above carbon nanotube powder:
firstly, adding 5g of carbon nano tube powder into 50ml of absolute ethyl alcohol, oscillating for 10min by using ultrasonic waves to uniformly disperse the carbon nano tube powder, standing and layering for 25min, then dripping 1ml of supernatant onto a copper mesh grid, and drying to obtain a sample;
then, scanning electron microscope analysis is carried out on the sample through a cold field emission scanning electron microscope, and the following steps are obtained: the number of the carbon nanotubes is large, the tube holes are uniformly distributed, impurity particles are not attached to the top ends of the carbon nanotubes, the outer diameter length of the tubes is estimated through scanning electron microscope analysis, and the outer diameter range of the tubes is estimated to be about 1nm according to the formula of the outer diameter range of the tubes = the outer diameter of the longest tube-the outer diameter of the shortest tube;
finally, performing transmission electron microscope analysis on the sample by using a transmission electron microscope to obtain: the carbon nano tube has good crystallinity, the carbon nano tube and the graphite layer have good collimation, the distance between two adjacent graphite sheets is estimated by a transmission electron microscope, and the graphite sheet distance range is about 0.05nm according to the formula of graphite sheet distance range = longest graphite sheet distance-shortest graphite sheet distance.
Example 3
The preparation process of the carbon nanotube with pentacarbonyl iron liquid as the material includes the following steps:
s1: dispersing pentacarbonyl iron liquid with absolute ethyl alcohol and mixing with organic modifier
Putting the mixing box into a circulating water tank, introducing circulating water at 20 ℃ into the circulating water tank to maintain the temperature inside the mixing box at 20 ℃, then adding 60ml of absolute ethyl alcohol and 1g of pentacarbonyl iron liquid into the mixing box together, stirring for 30min at a speed of 300r/min by using a stirrer, finally adding 2ml of organic modifier prepared by mixing triethylene glycol and tri-n-octyl phosphine oxide according to a mass ratio of 3:1 into the mixing box, adjusting the speed of the stirrer to 800r/min, continuing stirring for 2h, carrying out ultrasonic treatment for 10min by using an ultrasonic probe, and uniformly mixing to obtain pentacarbonyl iron dispersion;
s2: atomized and collided with carbon monoxide
Adding the pentacarbonyl iron dispersion liquid into an atomizer, atomizing the pentacarbonyl iron dispersion liquid into mist droplets through the atomizer, spraying hydrogen with the flow rate of 0.4L/min and the flow rate of 0.3m/s into the atomizer through a first compression spray gun, carrying the mist droplets through the hydrogen and spraying the mist droplets into a mixing bin from the left side of the mixing bin, and simultaneously spraying carbon monoxide into the mixing bin from the right side of the mixing bin through a second compression spray gun with the flow rate of 0.6L/min and the flow rate of 0.4m/s, wherein the hydrogen carries the mist droplets to collide with the carbon monoxide in the mixing bin, and fully and uniformly mixing to obtain a mixed gas;
s3: providing acetylene and air premixed flame for pyrolysis
The method comprises the steps that helium is pressed into a mixing bin from bottom to top at 0.8L/min through an air pump, after the helium enters the mixing bin, the helium carries the mixed gas to continue to flow upwards until the helium passes through a central tube of a heating furnace and contacts a pressure sensor at an air inlet valve at the bottom of the heating furnace, when the pressure sensor detects that the pressure at the air inlet valve rises, the pressure sensor sends a signal to a controller, the controller receives the signal sent by the pressure sensor, controls the air inlet valve to be opened, controls a flame supplier at two sides of the heating furnace to respectively provide acetylene and air premixed flame for the furnace from two sides of the heating furnace at 0.8L/min and 3L/min, then the helium carries the mixed gas to enter a pyrolysis chamber of the heating furnace, the acetylene and the air premixed flame burns outside the pyrolysis chamber to provide a heat source for the pyrolysis chamber, and after pyrolysis for 5h, carbon nano tube mixed powder is obtained;
s4: adding hydrochloric acid to remove impurities and washing
After the carbon nano tube mixed powder is cooled to room temperature along with the furnace, a discharge valve of the heating furnace is opened, the carbon nano tube mixed powder is put into the filter until a gravity sensor in the filter detects that the gravity in the filter is not increased any more, the gravity sensor sends a signal to a controller, the controller receives the signal sent by the gravity sensor, controls a feeding component to add hydrochloric acid into the filter, simultaneously controls a stirring device in the filter to stir for 5 hours at the speed of 500r/min for impurity removal reaction, so as to obtain suspension, then controls the stirring device to stop stirring, controls the filter to start and controls a liquid outlet valve to open, filters the suspension until the filtrate is completely discharged, controls the liquid outlet valve to close, deionized water is added into the filter, the filter residue is washed for a plurality of times, the pH value of the discharged filtrate is detected after the filtrate is washed each time, until the pH value of the discharged filtrate is detected to be 7, the filter residue is stopped washing again, and the filter residue is put into an oven for drying, so as to obtain the carbon nano tube powder.
Then, experimental tests were performed on the above carbon nanotube powder:
firstly, adding 5g of carbon nano tube powder into 50ml of absolute ethyl alcohol, oscillating for 10min by using ultrasonic waves to uniformly disperse the carbon nano tube powder, standing and layering for 25min, then dripping 1ml of supernatant onto a copper mesh grid, and drying to obtain a sample;
then, scanning electron microscope analysis is carried out on the sample through a cold field emission scanning electron microscope, and the following steps are obtained: the number of the carbon nanotubes is large, the tube holes are uniformly distributed, impurity particles are not attached to the top ends of the carbon nanotubes, the outer diameter length of the tubes is estimated through scanning electron microscope analysis, and the outer diameter range of the tubes is estimated to be about 1nm according to the formula of the outer diameter range of the tubes = the outer diameter of the longest tube-the outer diameter of the shortest tube;
finally, performing transmission electron microscope analysis on the sample by using a transmission electron microscope to obtain: the carbon nano tube has good crystallinity and good collimation degree of the carbon nano tube and the graphite layer, the distance between two adjacent graphite sheets is estimated by a transmission electron microscope, and the graphite sheet distance range is about 0.02nm according to the formula of graphite sheet distance range = longest graphite sheet distance-shortest graphite sheet distance.
Comparative example 1
As shown in fig. 1 and 3, referring to the preparation steps of example 1, other conditions are unchanged, and only the organic modifier in step S1 is replaced by the same amount of absolute ethyl alcohol, namely, the pentacarbonyl iron liquid is dispersed in the absolute ethyl alcohol, and the organic modifier is not added, and then the carbon nanotube powder is prepared according to steps S2-S4 in example 1.
Then, experimental tests were performed on the produced carbon nanotube powder:
firstly, adding 5g of carbon nano tube powder into 50ml of absolute ethyl alcohol, oscillating for 10min by using ultrasonic waves to uniformly disperse the carbon nano tube powder, standing and layering for 25min, then dripping 1ml of supernatant onto a copper mesh grid, and drying to obtain a sample;
then, scanning electron microscope analysis is carried out on the sample through a cold field emission scanning electron microscope, and the following steps are obtained: the number of the carbon nanotubes is large, the tube holes are uniformly distributed, impurity particles are not attached to the top ends of the carbon nanotubes, the outer diameter length of the tubes is estimated through scanning electron microscope analysis, and the outer diameter range of the tubes is estimated to be about 8nm according to the formula of the outer diameter range of the tubes = the outer diameter of the longest tube-the outer diameter of the shortest tube;
finally, performing transmission electron microscope analysis on the sample by using a transmission electron microscope to obtain: the carbon nano tube has good crystallinity and good collimation degree of the carbon nano tube and the graphite layer, the distance between two adjacent graphite sheets is estimated by a transmission electron microscope, and the graphite sheet distance range is about 0.04nm according to the formula of graphite sheet distance range = longest graphite sheet distance-shortest graphite sheet distance.
As shown by the test results of the comparative example 1, the pentacarbonyl iron liquid is firstly mixed with absolute ethyl alcohol, and then the organic modifier triethylene glycol and tri-n-octyl phosphine oxide are uniformly mixed to prepare the pentacarbonyl iron dispersion liquid, so that the pentacarbonyl iron dispersion liquid is uniformly dispersed in the pyrolysis process after atomization, the number of carbon nanotubes prepared by pyrolysis is more, the pore distribution is uniform and the pore diameters are consistent, and the effect of improving the quality of the carbon nanotubes is achieved.
Comparative example 2
As shown in fig. 1 and 4, referring to the preparation steps of example 1, other conditions are unchanged, only the step S2 is replaced by adding the pentacarbonyl iron dispersion liquid prepared in the step S1 into an atomizer, atomizing the pentacarbonyl iron dispersion liquid into mist droplets by the atomizer, spraying hydrogen into the atomizer by a first compression spray gun, carrying the mist droplets by the hydrogen and spraying the mist droplets from the left side of a mixing bin to obtain a mixed vapor, storing the mixed vapor, then in the subsequent step S3, introducing helium into the mixing bin, carrying the mixed vapor into a pyrolysis chamber of a heating furnace, and additionally introducing carbon monoxide into the pyrolysis chamber for pyrolysis, wherein the difference between the step and example 1 is that the mist droplets are not collided and mixed with the carbon monoxide.
Then, experimental tests were performed on the produced carbon nanotube powder:
firstly, adding 5g of carbon nano tube powder into 50ml of absolute ethyl alcohol, oscillating for 10min by using ultrasonic waves to uniformly disperse the carbon nano tube powder, standing and layering for 25min, then dripping 1ml of supernatant onto a copper mesh grid, and drying to obtain a sample;
then, scanning electron microscope analysis is carried out on the sample through a cold field emission scanning electron microscope, and the following steps are obtained: the number of the carbon nanotubes is large, the tube hole distribution is uniform, impurity particles are not attached to the top end of the carbon nanotubes, the outer diameter length of the tubes is estimated through scanning electron microscope analysis, and the outer diameter range of the tubes is estimated to be about 2nm according to the formula of the outer diameter range of the tubes = the outer diameter of the longest tube-the outer diameter of the shortest tube;
finally, performing transmission electron microscope analysis on the sample by using a transmission electron microscope to obtain: the crystallinity of the carbon nanotubes is poor, the collimation of the carbon nanotubes and the graphite layers is poor, the distance between two adjacent graphite sheets is estimated by a transmission electron microscope, and the graphite sheet distance range is about 1.32nm according to the formula of graphite sheet distance range = longest graphite sheet distance-shortest graphite sheet distance.
As shown by the experimental test results of comparative example 1, the atomized droplets of the iron pentacarbonyl dispersion liquid are carried by hydrogen and collide with and mix with carbon monoxide gas, so that the atomized droplets and carbon monoxide gas can be mixed more uniformly, the crystallinity of the prepared carbon nanotubes is better, the collimation degree of the carbon nanotubes and graphite sheets is better, and the spacing between the graphite sheets is uniform.
Comparative example 3
As shown in fig. 1 and 5, referring to the preparation procedure of example 1, other conditions are unchanged, and only the hydrochloric acid in step S4 is replaced with deionized water of equal amount.
Then, experimental tests were performed on the produced carbon nanotube powder:
firstly, adding 5g of carbon nano tube powder into 50ml of absolute ethyl alcohol, oscillating for 10min by using ultrasonic waves to uniformly disperse the carbon nano tube powder, standing and layering for 25min, then dripping 1ml of supernatant onto a copper mesh grid, and drying to obtain a sample;
then, scanning electron microscope analysis is carried out on the sample through a cold field emission scanning electron microscope, and the following steps are obtained: the number of the carbon nanotubes is large, the tube holes are uniformly distributed, impurity particles are attached to the top end of the carbon nanotubes, the outer diameter length of the tubes is estimated through scanning electron microscope analysis, and the outer diameter range of the tubes is estimated to be about 1nm according to the formula of the outer diameter range of the tubes = the outer diameter of the longest tube-the outer diameter of the shortest tube;
finally, performing transmission electron microscope analysis on the sample by using a transmission electron microscope to obtain: the carbon nano tube has good crystallinity, the carbon nano tube and the graphite layer have good collimation, the distance between two adjacent graphite sheets is estimated by a transmission electron microscope, and the graphite sheet distance range is about 0.03nm according to the formula of graphite sheet distance range = longest graphite sheet distance-shortest graphite sheet distance.
As can be seen from the experimental test results of comparative example 1, the carbon nanotube mixed powder prepared by pyrolysis was added to hydrochloric acid to react, so as to remove impurities, and washed with deionized water, thereby preparing higher purity carbon nanotubes.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (7)
1. The preparation process of the carbon nano tube with pentacarbonyl iron liquid as the raw material is characterized by comprising the following steps:
s1: dispersing pentacarbonyl iron liquid with absolute ethyl alcohol and mixing with organic modifier
Stirring and mixing absolute ethyl alcohol and pentacarbonyl iron liquid, adding an organic modifier prepared by mixing triethylene glycol and tri-n-octyl phosphine oxide according to a mass ratio of 1-3:1, stirring and mixing, and performing ultrasonic treatment to obtain pentacarbonyl iron dispersion;
s2: atomized and collided with carbon monoxide
Atomizing the pentacarbonyl iron dispersion liquid, carrying the pentacarbonyl iron dispersion liquid into a mixing bin by hydrogen, and carrying out collision mixing with carbon monoxide to obtain mixed gas;
s3: providing acetylene and air premixed flame for pyrolysis
Carrying the mixed gas into a pyrolysis chamber through helium, and then providing a heat source for the pyrolysis chamber through premixed flame of acetylene and oxygen for pyrolysis to obtain carbon nano tube mixed powder;
s4: adding hydrochloric acid to remove impurities and washing
Adding hydrochloric acid into the carbon nano tube mixed powder, stirring while performing impurity removal reaction, filtering, washing with deionized water, and drying to obtain carbon nano tube powder.
2. The process for preparing carbon nanotubes from iron pentacarbonyl solution of claim 1, wherein the anhydrous ethanol of step S1 disperses the iron pentacarbonyl solution and mixes with an organic modifier, comprising the steps of
S1.1: putting the mixing box into a circulating water tank, and then introducing 10-20 ℃ circulating water into the circulating water tank to maintain the inside of the mixing box at 10-20 ℃;
s1.2: adding the anhydrous ethanol and the pentacarbonyl iron liquid into a mixing box together according to the ratio of 50-60ml to 1g, and stirring for 20-30min at the speed of 200-300r/min by using a stirrer;
s1.3: adding an organic modifier prepared by mixing triethylene glycol and tri-n-octyl phosphine oxide according to the mass ratio of 20-30:1 into a mixing box, regulating the speed of a stirrer to 500-800r/min, continuously stirring for 1-2h, carrying out ultrasonic treatment for 5-10min by using an ultrasonic probe, and uniformly mixing to obtain the pentacarbonyl iron dispersion liquid.
3. The process for preparing carbon nanotubes from pentacarbonyl iron liquid according to claim 2, wherein the atomizing and collision mixing with carbon monoxide in step S2 specifically comprises the following steps:
s2.1: adding the iron pentacarbonyl dispersion liquid prepared in the step S1.3 into an atomizer, and atomizing the iron pentacarbonyl dispersion liquid into mist droplets through the atomizer;
s2.2: spraying hydrogen into the atomizer through the first compression spray gun, carrying mist droplets through the hydrogen and spraying into the mixing bin from the left side of the mixing bin, and simultaneously spraying carbon monoxide into the mixing bin from the right side of the mixing bin through the second compression spray gun;
s2.3: the atomized liquid drops carried by the hydrogen collide with the carbon monoxide in the mixing bin and are fully and uniformly mixed to obtain the mixed gas.
4. The process for preparing carbon nanotubes from pentacarbonyl iron liquid of claim 3, wherein step S3 of providing acetylene and air premixed flame for pyrolysis comprises the following steps:
s3.1: pressing helium into the mixing bin from bottom to top at the speed of 0.6-0.8L/min by an air pump, and carrying the mixed gas prepared in the step S2.3 to continuously flow upwards after the helium enters the mixing bin;
s3.2: until the pressure sensor passes through the central tube of the heating furnace and contacts the pressure sensor at the air inlet valve at the bottom of the heating furnace, when the pressure sensor detects that the pressure at the air inlet valve rises, the pressure sensor sends a signal to the controller;
s3.3: after receiving the signal sent by the pressure sensor, the controller controls the air inlet valve to be opened, and controls the fire feeders at two sides of the heating furnace to respectively provide acetylene and air premixed flames at 0.5-0.8L/min and 2-3L/min from two sides of the heating furnace;
s3.4: helium carries the mixed gas to enter a pyrolysis chamber of a heating furnace, acetylene and air premixed flame burns outside the pyrolysis chamber to provide a heat source for the pyrolysis chamber, and carbon nano tube mixed powder is obtained after pyrolysis for 3-5 hours.
5. The process for preparing carbon nanotubes from pentacarbonyl iron liquid of claim 4, wherein the adding hydrochloric acid of step S4 removes impurities and washes, specifically comprising the steps of:
s4.1: after the carbon nano tube mixed powder prepared in the step S3.4 is cooled to room temperature along with the furnace, a discharge valve of the heating furnace is opened, and the carbon nano tube mixed powder is put into a filter;
s4.2: until the gravity sensor in the filter detects that the gravity in the filter is no longer increased, the gravity sensor sends a signal to the controller;
s4.3: after the controller receives the signal sent by the gravity sensor, the feeding component is controlled to add hydrochloric acid into the filter, and meanwhile, the stirring device in the filter is controlled to stir for 3-5 hours at the speed of 400-500r/min, and impurity removal reaction is carried out to obtain suspension;
s4.4: the controller controls the stirring device to stop stirring, controls the filter to start and controls the liquid outlet valve to open, and filters the suspension;
s4.5: after the filtrate is completely discharged, the controller controls the liquid outlet valve to be closed, deionized water is added into the filter, the filter residue is washed for a plurality of times, and the pH value of the discharged filtrate is detected after the filtrate is discharged after washing each time;
s4.6: stopping washing again until the pH detector detects that the pH of the discharged filtrate is=6-7, and putting filter residues into a baking oven for baking to obtain the carbon nano tube powder.
6. The process for preparing carbon nanotubes using pentacarbonyl iron liquid as raw material of claim 5, wherein in the pyrolysis process of the heating furnace in step S3.4, the waste gas after pyrolysis is collected by the waste gas collecting box at the top of the heating furnace until the temperature sensor in the waste gas collecting box detects that the waste gas is cooled to 150-200 ℃, the temperature sensor sends a signal to the controller, and after receiving the signal sent by the temperature sensor, the controller controls the air pump to introduce the waste gas cooled in the waste gas collecting box into the oven in step S4.6, and the washed wet carbon nanotube powder is dried.
7. The process for preparing carbon nanotubes from iron pentacarbonyl solution of claim 3, wherein the hydrogen flow rate is 0.2-0.4L/min, the flow rate is 0.2-0.3m/s, the carbon monoxide flow rate is 0.5-0.6L/min, and the flow rate is 0.3-0.4m/s.
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| WO2020261891A1 (en) * | 2019-06-27 | 2020-12-30 | 東レ株式会社 | Carbon nanotube liquid dispersion, production method for semiconductor element using same, and production method for wireless communication device |
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| CN106672942A (en) * | 2017-01-18 | 2017-05-17 | 太原理工大学 | Preparation method of porous carbon nanotube |
| CN107720725A (en) * | 2017-11-22 | 2018-02-23 | 江西悦安超细金属有限公司 | A kind of method and device for preparing CNT |
| WO2019100949A1 (en) * | 2017-11-22 | 2019-05-31 | 江西悦安超细金属有限公司 | Method and device for preparing carbon nanotube and carbon nanotube prepared thereby |
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